Aqueous silicone/(CO) polymer dispersions crosslinkable into elastomeric state

ABSTRACT

Aqueous silicone dispersions crosslinkable into elastomeric state on removal of water therefrom under ambient conditions, well adapted, e.g., for the production of elastomeric silicone seals in the construction industry, include an oil-in-water base emulsion (A) of an α,ω-(dihydroxy) polydiorganosiloxane stabilized with at least one anionic or nonionic surface-active agent, or mixture thereof, (B) an aqueous latex of an organic (co)polymer having a particle size ranging from 0.01 to 0.5 μm and a solids content ranging from 20% to 70% by weight, (C) an effective crosslinking amount of at least one crosslinking agent, (D) an effective amount of at least one nonsiliceous filler material, and (E), optionally, a catalytically effective amount of a metal curing catalyst, such aqueous dispersions further having a solids content of at least 40% by weight.

This application is a divisional of application Ser. No. 07/541,301,filed Jun. 18, 1990 now U.S. Pat. No. 5,360,851.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel aqueous dispersions based on asilicone and an organic polymer latex, such novel aqueous dispersionsbeing crosslinkable into elastomeric state upon removal of watertherefrom.

2. Description of the Prior Art

Silicone-based aqueous dispersions crosslinkable into elastomeric stateon removal of water therefrom are known to this art. These comprise:

(a) an emulsion (A) of the oil-in-water type of anα,ω-(dihydroxy)polydiorganosiloxane, stabilized with an anionic and/ornonionic surfactant;

(b) a crosslinking agent;

(c) a nonsiliceous inorganic filler; and

(d) a curing catalyst.

The base emulsion contains a reactive silicone oil having silanolendgroups, which is generally polymerized in emulsion according to thetechnique described in U.S. Pat. Nos. 2,891,920, 3,294,725 and3,360,491, namely, using an anionic surfactant which preferably alsoserves as the polymerization catalyst.

EP-A-327,321 describes an aqueous dispersion of the above type, in whichthe base emulsion is a mixture of a macroemulsion of a reactive siliconeoil and a microemulsion of a reactive silicone oil having a particlesize of less than 0.14 μm. A dispersion of this type presents the twindisadvantage of being costly and of crosslinking on evaporation of waterinto an elastomer exhibiting insufficient adhesiveness to substratesand/or mediocre mechanical properties.

In this general type of aqueous dispersion that crosslinks intoelastomeric state on removal of water, the literature indicates theoption of using a wide variety of crosslinking agents for the baseemulsion, among which are:

(i) colloidal silica (U.S. Pat. Nos. 3,294,725 and 4,221,688);

(ii) sodium silicate (U.S. Pat. No. 4,244,849);

(iii) an amorphous silica powder (FR-A-2,463,163);

(iv) a microemulsion of a silsesquioxane resin (U.S. Pat. No.3,355,406);

(v) a siliconate (EP-A-266,729, EP-A-332,544 and EP Application89/4,200,567, filed Feb. 16, 1989 and assigned to the assignee hereof);

(vi) a reactive silicone resin of low molecular weight, containingalkoxy or acyloxy groups (U.S. Pat. No. 4,554,187;

(vii) a silicone resin of high molecular weight, insoluble in toluene(EP-A-304,719);

(viii) a polyalkoxysilane, a polysilicate, a polyacyloxysilane or apolyketiminoxysilane (U.S. Pat. Nos. 3,294,725, 4,584,341, 4,618,642 and4,608,412);

(ix) a polyamino-- (or amido)silane (Application FR-A-89/01,654, filedFeb. 3, 1989 and assigned to the assignee hereof);

(x) a polyalkenoxysilane (Application FR-A-88/13,618, filed Oct. 11,1988 and assigned to the assignee hereof);

(xi) a hydroxylated silicone resin containing, per molecule, at leasttwo siloxy units selected from among those of the formulae: R₃ SiO₀.5(M), R₂ SiO (D), RSiO₁.5 (T) and SiO₂ (Q) (Application FR-A-88/11,609,filed Aug. 31, 1988 and also assigned to the assignee hereof).

These aqueous dispersions are typically catalyzed using a curingcatalyst which is, preferably, a tin salt, and which may also be thecombination of a tin salt and boric acid (U.S. Pat. No. 4,863,985).

However, these aqueous dispersions present many disadvantages, the mostnotable of which being:

(1) Insufficient storage stability;

(2) Mediocre adhesiveness to many substrates, in particular thoseemployed in the construction industry (glass, concrete, metals, steel,aluminum, thick plastic coatings such as PVC, limestone, and the like);

(3) Paints prepared from these aqueous dispersions exhibit a bindingpower and a resistance to abrasion, in particular to wet abrasion, whichmay be insufficient;

(4) Elastomers produced from these aqueous dispersions on evaporation ofwater exhibit a very high shrinkage, associated with a modulus ofelasticity (ME) and a tearing strength (TrS) which are too low forcertain applications;

(5) Excessively high viscosity of silicone emulsions having high solidscontents which are required for formulating filled aqueous dispersionsof low volume extract.

Furthermore, organic (co)polymer latex aqueous dispersions, for exampleof alkyl (meth)acrylate and of vinyl esters of monocarboxylic acids,have long been used as paints to provide thin coatings or thickcoatings, in particular in the construction industry for waterproofingfacades and roofing.

These aqueous dispersions typically present the following disadvantages:

(1') The coating formed exhibits an insufficient permeability to gasesand in particular to water vapor;

(2') The viscosity of the aqueous dispersion is too low and itsfilm-forming capacity may be insufficient;

(3') The coatings obtained are too water-sensitive and insufficientlywater-repellent;

(4') The coatings obtained are sensitive to actinic radiation and inparticular to UV.

The patent literature has also described the combination of a siliconeand an organic latex;

FR-A-2,526,033 and U.S. Pat. Nos. 4,012,355 and 2,739,910 describe thecombination of a siliconate and an organic polymer latex;

DE-A-2,355,813 describes a system in which the siliconate may bereplaced by a silicone resin emulsion; according to CH-A-61,842 both thesiliconate and a silicone resin are associated with an acrylic acidcopolymerizate.

None of these documents describes the further use of an emulsion of asilicone oil having silanol endgroups, of nonsiliceous filler and ofcuring catalysts.

EP-A-246,537 describes the preparation, in latex form, of a laminatedelastomeric material of the following three elements:

(i) a core of crosslinked silicone rubber;

(ii) a first sheath of crosslinked acrylic rubber; and

(iii) a second sheath obtained by radical (co)polymerization ofresin-forming monomers.

SUMMARY OF THE INVENTION

Accordingly, a major object of the present invention is the provision ofnovel aqueous dispersions of silicone and of an organic polymer latexwhich present the cumulative advantages of aqueous silicone dispersionsand aqueous organic polymer dispersions, and even synergistic results inthe case of certain desirable properties.

Another object of the present invention is the provision of noveldispersions of the above type which do not present the disadvantagesinherent in dispersions of silicones alone or dispersions of organicpolymers alone, or which novel dispersions conspicuously ameliorate saiddisadvantages, which is acceptable in the majority of the uses of suchdispersions.

Yet another object of this invention is the provision of noveldispersions of the above type which, after crosslinking, optionallyexhibit the following properties at the same time:

(1) A storage stability of at least six months, preferably at least oneyear;

(2) A viscosity of the unfilled material and of the material packaged ina cartridge which is suitable even in the event of aqueous dispersionswhich have a high solids content of more than 75%, these dispersionsproducing elastomers of relatively low modulus;

(3) A satisfactory adhesiveness to the widest variety of substrates,e.g., stone, concrete, mortar, metals, steel, aluminum, fibro-cement,enamels, ceramics and plastics such as PVC;

(4) A suitable viscosity, endowing them with an extrudability from thepackaging cartridge and a suitable film-forming capacity;

(5) A suitable resistance to abrasion, in particular to wet abrasion, toatmospheric moisture and to actinic radiations (visible light, UV);

(6) Good permeability to gases and to water vapor;

(7) Satisfactory mechanical properties, in particular as regards modulusof elasticity and tear strength;

(8) A satisfactory water-repellency.

Briefly, the present invention features aqueous dispersions based on asilicone that are crosslinkable into elastomeric state upon removal ofwater therefrom under ambient conditions, comprising, by weight:

(A) 100 parts of an oil-in-water emulsion of anα,ω-(dihydroxy)polydiorganosiloxane, stabilized with at least onesurface-active agent selected from among the anionic and nonionicsurface-active agents and mixtures thereof;

(B) 2 to 80, preferably 3 to 40, parts of an aqueous dispersion of anorganic (co)polymer which has a particle size ranging from 0.07 to 0.5μm, preferably from 0.05 to 0.2 μm, and a solids content ranging from20% to 70% by weight;

(C) an effective amount of at least one crosslinking agent;

(D) 5 to 200, preferably 50 to 150, parts of a nonsiliceous inorganicfiller;

(E) optionally, 0.01 to 3 parts by weight of a metal curing catalyst,and said dispersions having a dry solids content of at least 40%.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

More particularly according to the present invention, the final aqueousdispersion is prepared simply by thoroughly mixing all of theconstituents thereof, resulting in a homogeneous dispersion which isstable in storage in the absence of air.

The Emulsions (A)

The α,ω-(dihydroxy)polydiorganosiloxanes must have a viscosity of atleast 100 mPa.s at 25° C., preferably of at least 50,000 mPa.s.

Indeed, it is in the case of viscosities above 50,000 mPa.s that anelastomer is produced which exhibits a combination of suitablemechanical properties, in particular with regard to Shore A hardness andelongation.

In addition, the higher the viscosity, the more the mechanicalproperties are preserved when the elastomer is aged.

According to the present invention, the preferred viscosities range from50,000 to 1,500,000 mPa.s at 25° C.

The organic radicals of the α,ω-(dihydroxy) polydiorganopolysiloxanesare monovalent hydrocarbon radicals having up to 6 carbon atoms,optionally substituted by cyano or fluoro groups. The radicals which aretypically employed, because of their presence in the commerciallyavailable siloxanes, are methyl, ethyl, propyl, phenyl, vinyl and3,3,3-trifluoropropyl radicals. At least 80% of the number of theseradicals are generally methyl radicals.

In a preferred embodiment of the present invention,α,ω-(dihydroxy)polydiorganopolysiloxanes are used that have beenprepared by the anionic polymerization technique described in the aboveU.S. Pat. No. 2,891,920 and especially U.S. Pat. No. 3,294,725, herebyincorporated by reference. The polymer obtained is stabilizedanionically with a surface-active agent which, according to U.S. Pat.No. 3,294,725, is preferably the alkali metal salt of an aromatichydrocarbon sulfonic acid, the free acid also serving as thepolymerization catalyst.

The preferred catalyst and surface-active agent aredodecylbenzenesulfonic acid and its alkali metal salts, in particularits sodium salt. Other anionic or nonionic surface-active agents mayoptionally be added. However, this addition is not necessary because, inaccordance with U.S. Pat. No. 3,294,725, the amount of anionicsurface-active agent resulting from the neutralization of the sulfonicacid is sufficient to stabilize the polymer emulsion. This amount iftypically less than 3%, preferably 1.5% of the weight of the emulsion.

This emulsion polymerization process is of particular interest becauseit permits the direct preparation of the emulsion (A). Moreover, thisprocess permits the option of easily obtainingα,ω-(dihydroxy)polydiorganosiloxane emulsions (A) of very highviscosity.

To prepare the emulsion (A), it is also possible to begin with alreadypolymerized α,ω-(dihydroxy)polydiorganosiloxane, and then to convert itinto an aqueous emulsion, stabilizing the emulsions with an anionicand/or nonionic surface-active agent according to technique which iswell known to this art and abundantly described in the literature (see,for example, FR-A-2,064,563, FR-A-2,094,322, FR-A-2,114,230 andEP-A-169,098.

According to this process, the α,ω-(dihydroxy)-polydiorganosiloxanepolymers are mixed with the anionic or nonionic surface-active agentsimply by stirring, it being possible for the latter material to be inaqueous solution, then to add water, if necessary, and to convert theentire mass into a fine and homogeneous emulsion by passing it through aconventional colloid mill.

The millbase obtained is subsequently diluted with an appropriate amountof water and a storage-stable emulsion (A) stabilized with an anionic ornonionic surface-active agent is thus obtained.

The amount of anionic and nonionic surface-active agent which can beemployed is that commonly used in the emulsification process, inparticular those described in the aforementioned patents and in U.S.Pat. No. 2,891,920.

The anionic surface-active agents which are preferred according to thepresent invention are the alkali metal salts of an aromatic hydrocarbonsulfonic acid and the preferred nonionic surface-active agents arepolyoxyethylenated alkylphenols. These nonionic surface-active agentsare, of course, the same as those which can optionally be added to theemulsions (A) produced by emulsion polymerization, as indicated above.

The emulsion (A) prepared by emulsion polymerization or by emulsifyingthe silicone polymer is in the form of an oil-in-water emulsion andpreferably has a solids content of at least 40% by weight.

The Dispersion (B)

This is a "latex" formulated from an aqueous dispersion of polymerparticles resulting from conventional processes of emulsion(co)polymerization of polymerizable organic monomers. These organicmonomers are preferably selected from among:

(a) Alkyl (meth)acrylates, the alkyl moiety of which preferably has from1 to 18 carbon atoms, in particular methyl acrylate, ethyl acrylate,propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate,lauryl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, octylacrylate, methyl methacrylate, chloroethyl methacrylate, butylmethacrylate, 3,3-dimethylbutyl methacrylate, ethyl methacrylate,isobutyl methacrylate, isopropyl methacrylate, phenyl methacrylate,butyl chloroacrylate, methyl chloroacrylate, ethyl chloroacrylate,isopropyl chloroacrylate and cyclohexyl chloroacrylate;

(b) α,β-Ethylenically unsaturated esters of monocarboxylic acids, theacidic moiety of which is nonpolymerizable and the unsaturated moietypreferably has from 2 to 14 carbon atoms and the acidic moiety from 2 to12 carbon atoms, in particular vinyl acetate, vinyl propionate, vinylbutyrate, allyl acetate, vinyl versatate® (registered trademark foresters of C₉ -C₁₁ α-branched acids), vinyl laurate, vinyl benzoate,vinyl trimethylacetate, vinyl pivalate and vinyl trichloroacetate;

(c) The esters and half-esters of α,β-ethylenically unsaturatedpolycarboxylic acids having from 4 to 24 carbon atoms, in particulardimethyl fumarate, diethyl maleate, methyl ethyl fumarate and2-ethylhexyl fumarate;

(d) Vinyl halides, in particular vinyl chloride, vinyl fluoride,vinylidene chloride and vinylidene fluoride;

(e) Vinylaromatic compounds preferably having not more than 24 carbonatoms and selected in particular from among styrene, α-methylstyrene,4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene,2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene,3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene,4-chloro-3-methylstyrene, 4-tert-butylstyrene, 4-dichlorostyrene,2,6-dichlorostyrene, 2,5-difluorostyrene and 1-vinylnaphthalene.

(f) Conjugated aliphatic dienes preferably having from 3 to 12 carbonatoms, in particular 1,3-butadiene, isoprene and 2-chloro-1,3-butadiene;

(g) α,β-ethylenically unsaturated nitriles preferably having from 3 to 6carbon atoms, such as acrylonitrile and methacrylonitrile.

Polystyrene latices and polyvinylacetate latices are particularlyrepresentative homopolymer latices.

Dispersions (B) which can be used according to the present inventionare, for example, those containing a copolymer obtained bycopolymerization:

(i) of a monomer (a) and of a monomer (b), such as copolymers of thevinyl acetate/alkyl acrylate type;

(ii) of a monomer (a), of a monomer (b) and of a monomer (c), such as,for example, a terpolymer of the acetate/acrylate/maleate type;

(iii) of a monomer (b), of a monomer (d) and of an olefinic monomer,such as, for example, the acetate/vinyl chloride/ethylene terpolymer;

(iv) of a monomer (e) and of a monomer (a), among which styrene/alkylacrylate copolymers in which the styrene/alkyl acrylate weight ratioranges from 30/70 to 70/30 are very particularly representative;

(v) of a monomer (e) and of an α,β-ethylenically unsaturated carboxylicacid preferably having from 4 to 12 carbon atoms, including mono- andpolycarboxylic acids such as (meth)acrylic acids, itaconic acid, maleicacid, fumaric acid, such as the styrene/methacrylic acid copolymer;

(vi) of a monomer (e), of an α,β-ethylenically unsaturated carboxylicacid indicated above and of a monomer (g), such as thestyrene/acrylonitrile/itaconic acid copolymers;

(vii) of a monomer (e) and of a monomer (f).

In addition to the principal monomers (e) to (g) indicated above, it ispossible to copolymerize certain of these principal monomers with up to15% by weight of other monomers that are ionic in character, inparticular:

(1) an α,β-ethylenically unsaturated carboxylic acid monomer indicatedabove, including mono- and polycarboxylic acids (acrylic, methacrylic,maleic, itaconic, fumaric and similar acids);

(2) an ethylenic monomer containing secondary, tertiary or quaternizedamine groups (vinylpyridines, diethylaminoethyl methacrylate, etc.);

(3) a sulfonated ethylenic monomer (vinyl sulfonate, styrenesulfonate,etc.);

(4) a zwitterionic ethylenic monomer (sulfopropyl-(dimethylaminopropyl)acrylate); or nonionic in character, in particular:

(5) amides of unsaturated carboxylic acids (acrylamide, methacrylamide,etc.);

(6) esters of (meth)acrylates and of polyhydroxypropyl orpolyhydroxyethylated alcohols.

The stabilization of the polymer particles within the aqueousdispersions is ensured either by the aforesaid comonomers of ionic ornonionic character, or by emulsifiers (surfactants), which arepreferably nonionic, such as polyethoxylated fatty alcohols,polyethoxylated alkylphenols and polyethoxylated fatty acids, or anionicsuch as alkylsulfates, alkylsulfonates or alkylarylsulfonates (inparticular dodecylbenzenesulfonate and dialkylsulfosuccinates).

The above aqueous dispersions of organic polymers are abundantlydescribed in the literature. According to this invention, theyadvantageously have a solids content which generally ranges from 20% to70% by weight and a particle size ranging from 0.01 to 0.5 μm,preferably from 0.05 to 0.30 μm.

The aqueous dispersions (B) in which the particle size is small, belowapproximately 0.15 μm, make it possible, in fact, to increase the solidscontent of the aqueous dispersions in a cartridge while preserving asuitable viscosity. After evaporation of water, these final aqueousdispersions produce elastomers of low modulus and of lower volumeshrinkage.

In order to produce an elastomer of this type, the aqueous dispersionaccording to the invention, resulting from the mixing of the emulsion(A) and of the dispersion (B), preferably has:

(i) a "twin population" particle size distribution, namely, a firstpopulation of particles preferably originating essentially from thedispersion (B) whose particle size ranges from approximately 0.01 μm to0.15 μm, preferably 0.10 μm, and a second population of particlesoriginating preferably essentially from the emulsion (A) and exhibitinga particle size ranging from 0.15 μm to 100 μm, generally from 0.20 μmto 5 μm;

(ii) a solids content of more than 60% by weight, preferably more than70% by weight;

(iii) a viscosity of less than 50,000 mPa.s at 25° C., measured at ashear rate of 1 s⁻¹, prior to the incorporation of the fillers (D), suchas to provide a final dispersion which can easily be extruded from thestorage cartridge.

To prepare such twin-population dispersions, it is particularlyadvantageous to carry out the emulsion polymerization of the emulsion(A) in the presence of the dispersion (B) in the case where thisdispersion (B) has a low solids content of, for example, from 20% to 40%by weight.

Film-forming or nonfilm-forming latices (dispersion B) may be employedaccording to the present invention.

By "film-forming" latex is intended a latex whose polymer particlescoalesce to form a film at the temperature of application of the finaldispersion. This temperature can range from 5° to 45° C. It is generallyabout 20° C. Conversely, by "non-film-forming" latices are intendedthose whose polymer particles remain as discrete entities in the finalmaterial and do not coalesce at the temperature of application of thefinal dispersion, i.e., during the evaporation of water and itsconversion into elastomer.

The preparation of film-forming or nonfilm-forming latices (see, inparticular, U.S. Pat. No. 3,819,557 in the case of nonfilm-forminglatices) is well known to this art and entails monomer(s) selection,adapting the emulsion polymerization process and optionally adding asolvent. To obtain a nonfilm-forming latex, it is generally sufficientfor the organic (co)polymer to have a glass transition temperature whichis higher than the temperature of formation of the elastomer from thefinal dispersion, namely, higher than 45° C. However, the use of afilm-forming latex is preferred, because the end result is an elastomerwhich has improved flexibility properties.

The Crosslinking Agent (C)

During the crosslinking of the aqueous dispersion, the crosslinkingagent permits reticulation of the elastomeric lattice bypolycondensation reactions between the reactive groups of thecrosslinking agent and the silanol endgroups of the silicone oil of theemulsion (A).

As described in the patents indicated above, there exist many differentcrosslinking agents which can be employed by themselves or mixed. Theamounts of crosslinking agents to be introduced into the aqueousdispersion depend precisely on the nature of the crosslinking agentemployed.

By "effective amount" of (C) is intended an amount which enablesproduction of an elastomer.

Exemplary crosslinking agents are indicated below, with the recommendedamounts in the final dispersion, such amounts being expressed in partsby weight per 100 parts of emulsion (A):

(i) 0.1 to 10 parts of colloidal silica;

(ii) 0.5 to 10 parts of sodium silicate;

(iii) 1 to 15 parts of silica powder selected from pyrogenic or fumedsilicas and precipitated silicas;

(iv) 0.1 to 15 parts, preferably 1 to 10 parts of an organosiliconate;

(v) 1 to 100 parts of a silsesquioxane resin microemulsion according tothe combined teachings of U.S. Pat. Nos. 3,355,406 and 3,433,780;

(vi) 5 to 100 parts of a reactive silicone resin of low molecularweight, containing alkoxy and acyloxy groups;

(vii) 5 to 100 parts of a silicone resin of high molecular weight,insoluble in toluene;

(viii) 5 to 100 parts of a hydroxylated silicone resin containing, permolecule, at least 2 different units selected from those of theformulae: R₃ SiO₀.5 (M), R₂ SiO (D), RSiO₁.5 (T) and SiO₂ (Q), Rpreferably being a C₁ -C₆ alkyl, vinyl and 3,3,3-trifluoropropylradical, and having a weight content of hydroxyl groups of from 0.1% to10%; among these resins, which are introduced as such or in the form ofaqueous emulsions, representative are MQ, MDQ, TD and MTD resins;

(ix) 1 to 20 parts of a silane of the formula:

    R.sub.a SiX.sub.4-a

in which R is a monovalent organic radical, in particular methyl orvinyl a is 1 or 0, and X is a condensable and/or hydrolyzable grouppreferably selected from among alkoxy, acyloxy, ketiminoxy, alkylamino,amido and alkenyloxy groups.

In the case where X is alkoxy, it is desirable to add2-amino-2-methylpropanol as stabilizer, according to EP-A-259,734.

The Nonsiliceous Inorganic Filler (D)

Another constituent of the dispersion according to the invention is 5 to200, preferably 10 to 150, parts by weight of an inorganicsemireinforcing or packing filler (D).

The fillers (D) advantageously have a particle size which typicallyranges from 0.001 to 300 μm and a BET surface area of less than 100 m²/g.

Exemplary fillers (D) which can be employed by themselves or mixed arecarbon black, titanium dioxide, aluminum oxide, hydrated alumina,expanded vermiculite, unexpanded vermiculite, hydrated borax, calciumcarbonate, zinc oxide, mica, talc, iron oxide, barium sulfate and slakedlime. Precipitated calcium carbonate having a mean particle diameter ofless than 0.1 μm is an example of a preferred nonsiliceous inorganicfiller (D).

These fillers (D) are introduced into the emulsion in the form of drypowder, for example simply by mixing.

According to an alternative embodiment of the invention, it has beenfound that if the filler (D) consists essentially only of a fillerselected from among hydrated alumina, expanded, vermiculite, unexpandedvermiculite and hydrated borax in an amount of 5 to 200, preferably of50 to 150, parts per 100 parts of emulsion (A), then an elastomer isproduced which has a particularly high flame resistance which cannot beattained from the other above-mentioned categories of filler (D), inparticular with aluminum oxide or unhydrated alumina. Ceramic or aramidfibers can also be incorporated, according to EP-A-212,827.

In another alternative embodiment, it is possible to incorporate, per100 parts by weight of the emulsion (A), a siliceous additive (F)selected from sodium silicate (0.3 to 30 parts), and a reinforcing orsemireinforcing siliceous filler (1 to 100 parts), insofar, of course,as this siliceous additive has not already been selected as thecrosslinking agent (C).

These siliceous fillers are selected from among colloidal silica,pyrogenic and precipitated silica powders, or mixtures thereof.Pyrogenic silica is preferred. Semireinforcing siliceous fillers, suchas diatomaceous earths or ground quartz can, however, also be employed.

The sum of the parts of (D)+(F) must be less than 350 parts by weightper 100 parts by weight of emulsion (A).

The pyrogenic and precipitated silica powders are well known to thisart; in particular, they are employed as fillers in silicone elastomercompositions heat-vulcanizable into a silicone rubber. These powdershave a mean particle size which is typically less than 0.1 μm and a BETspecific surface area of more than 50 m² / g, preferably ranging from150 to 350 m² /g.

The incorporation of this siliceous additive (F) in the emulsion (A) byany suitable means, in particular by stirring, considerably increasesthe viscosity of the emulsion (A), which is then pasty in nature.

Indeed, it has now been found according to the present invention thatthe addition of this siliceous additive (F) is sufficient to impart amore or less pronounced "thixotropic" nature to the emulsion. Theemulsion extracted, for example from a storage cartridge, adhereswithout flowing, even on a vertical substrate, and cures intoelastomeric state on evaporation of water therefrom at room (ambient)temperature. A nonflowing emulsion can also be obtained by using asfiller (D) calcium carbonate, the mean particle diameter of which isless than 0.1 μm.

The Metal Curing Catalyst (E)

The compound (E) is optional, in particular in the case of certaincrosslinking agents (C) such as a siliconate, but it is preferred to usethe catalyst (E) according to the present invention.

The metal curing catalyst compounds (E) are advantageously carboxylicacid salts and halides of metals selected from among lead, zinc,zirconium, titanium, iron, tin, barium, calcium and manganese.

The constituent (E) is preferably a tin catalyst compound, typically anorganotin salt, preferably introduced in the form of an aqueousemulsion. The organotin salts which can thus be used are described, inparticular, in the text by Noll, Chemistry and Technology Silicones,Academic Press, page 337 (1968).

It is also possible to use the product of reaction of an alkyl silicateor of an alkyl trialkoxysilane with dibutyltin diacetate, as describedin BE-A-842,305.

The preferred tin salts are tin bischelates (EP-A-147,323 andEP-A-235,049), diorganotin dicarboxylates and in particular dibutyl- ordioctyltin diversatates (GB-A-1,289,900), dibutyl- or dioctyltindiacetate, and dibutyl- or dioctyltin dilaurate. From 0.01 to 3,preferably from 0.05 to 2, parts by weight of organotin salt areemployed per 100 parts by weight of (A).

The aqueous dispersions according to the invention may additionallycomprise the usual additives and adjuvants such as, especially,fungicides, antifoams, antifreezes such as ethylene glycol and propyleneglycol, and thixotropic agents such as carboxymethyl cellulose, xanthangum and polyvinyl alcohol, dispersing agents (phosphates) orplasticizers (unreactive silicone oils or organic plasticizers such asalkylbenzenes having a molecular weight of more than 200).

To prepare the aqueous dispersions according to the invention, it isadvantageous to add to the emulsion (A) at room temperature, withstirring, first the dispersion (B) and then the crosslinking agent (C),optionally in the form of a dispersion or of an aqueous emulsion, thenthe metal curing catalyst (E) and lastly the nonsiliceous inorganicfiller (D) and, optionally, the siliceous additive (F).

The pH of the aqueous dispersion may be acidic, neutral or basic.Nevertheless, it is advantageous to adjust the pH of the dispersion to avalue ranging from 8 to 13 by means of a strong inorganic or organicbase (triethanolamine, sodium hydroxide, potassium hdyroxide).

The final dispersion obtained is homogenized and is then degassed andsubsequently packaged in a container or package which is sealed againstatmospheric oxygen and water vapor.

The constituents (A), (B), (C), (D) and (E) and optionally (F) are mixedin such amounts that the final emulsion has a solids content of morethan 40%, preferably more than 60%, but generally less than 90%. Thepreferred pH range is from 8 to 13.

The dispersions according to the invention can be employed as a paintcapable of being crosslinked in a thin layer. Such paints preferablyhave a solids content ranging from 40% to 70%.

To determine the solids content, 2 g of dispersion are placed in analuminum weighing dish and this is heated for one hour at 150° C. in anoven provided with air circulation. After cooling, the dish is weighedagain and the remaining material is determined as a percentage of theinitial 2 g, which represents the solids content.

In a preferred embodiment, after preparation thereof, the dispersionaccording to the invention is subjected to a stage of aging at roomtemperature, for from a few hours to several days.

This aging stage simply entails permitting the dispersion to standprotected against atmospheric oxygen before it is employed.

The dispersions according to the invention can be employed for theproduction of silicone elastomer seals, in particular for theconstruction industry and as water-repellent coatings for structuralsurfaces in contact with inclement weather, in a proportion, forexample, of 20 to 100 g of dispersion per m² of surface to be coated.

These dispersions can also be employed for coating variouspharmaceutical or plant-protection active substances formulated in asolid form (pastilles, tablets, pills and the like), for coating corkstoppers employed for sealing bottles of wines and of spirits, forcoating kitchenware and, in general, articles in contact with foodstuffs(for example bread molds).

Known coating techniques can be employed, in particular techniques ofcoating with a brush and by dipping (by immersion), spraying techniques,fluidized bed coating techniques and immersion coating techniques.

In the case of coatings for cork stoppers, a recommended technique isthe dip-coating technique, which entails immersing the stoppers in thedispersion, which wets the surface of the stopper, and then evaporatingoff the water.

The coating obtained represents 20 to 50 mg of elastomer per 100 cm² ofstopper surface. This layer makes it easier for the stopper to slide inthe neck of the bottle during the bottling and prevents "running",namely, leakages of liquid between the neck and the stopper.

The dispersions according to the invention can also be employed incosmetology in the case where their pH is consistent with the particularintended application.

Thus, the dispersions can be incorporated into cosmetic compositions forthe treatment of hair, especially for permanent waving with a view tocreating a porous elastomeric film on the strands of hair, according toEP-A-240,349 and EP-A-240,350, hereby incorporated by reference.

The dispersions can also be employed in face mask cream compositions andalso for producing dermocopies (reproduction of the skin in relief).

Finally, the dispersions according to the invention can be used ashair-removal compositions as described in U.S. Pat. No. 4,734,099,hereby also incorporated by reference.

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative.

EXAMPLE 1

An emulsion (A) was prepared by polymerizing 1,000 g of anα,ω-(dihydroxy)polydimethylsiloxane oil having a viscosity of 100 mPa.sat 25° C. in the presence of 30 g of dodecylbenzenesulfonic acid and 50g of Cemulsol® ON 10/20, marketed by Rhone-Poulenc, which is a nonionicsurfactant, namely, a polyoxyalkylenated compound containingapproximately 10 ethylene oxide units and 20 propylene oxide units.

The emulsion polymerization was terminated by neutralizing the catalystwith 14.5 g of triethanolamine when the viscosity of the oil reached55,000 mPa.s at 25° C.

The resulting emulsion (A) had a solids content of 60%.

In the case of each additive, the following were incorporated understirring for 10 minutes in 131 parts of emulsion (A):

(i) 40 parts of a styrene/butyl acrylate latex forming a film at roomtemperature, marketed by Rhone-Poulenc under the trademark Rhodopas®DS910, and having the following characteristics:

Solids content: 50%

pH: 8

Brookfield viscosity (500 revolutions/min): 4,500 mPa.s

Minimum film formation temperature: 16° C.

Particle diameter: 0.1 μm

Density of the dispersion: 1.032 g/cm³

Density of the polymer: 1.068 g/cm³

Refractive index of the polymer at 25° C.: 1,532;

(ii) 7 parts of an aqueous solution of potassium methylsiliconate havinga solids content of 40%;

(iii) 2.6 parts of an aqueous emulsion containing 37% by weight ofdi-n-octyltin dilaurate;

(iv) 80 parts of precipitated CaCO₃ having a mean particle size of 70nanometers.

The final dispersion had a solids content of 70% and a pH of 9.

After 7 days of storage, the dispersion was spread with a doctor bladeinto a 2-mm thick film, which was permitted to dry at room temperature(20° C.) for 10 days.

The following average mechanical properties were measured on a firstbatch of dried films:

(a) the Shore A hardness (SAH) according to ASTM Standard D-2240;

(b) the tensile strength (TS) according to AFNOR Standard T-46 002,corresponding to ASTM Standard D 412, in MPa;

(c) the elongation at break (EB) in % according to AFNOR Standard T 46002;

(d) the elasticity modulus (EM) at 100% elongation according to AFNORStandard T 46 002, in MPa.

The mechanical properties obtained are reported in Table 1 below.

To assess adhesiveness, a 4-mm thick bead of aqueous dispersion wasdeposited onto a glass or concrete support. After 12 days, theadhesiveness of the elastomer formed was assessed by pulling the bead byhand.

The adhesions were qualified in three ways:

(1) good adhesiveness when the bead could not be stripped from itssupport (indicated as ++);

(2) average adhesiveness when the bead is stripped with difficulty andover small surfaces (indicated as +);

(3) absence of adhesiveness when the bead is stripped easily (indicatedas 0).

The assessments of the adhesion are reported in Table 1 below.

COMPARATIVE EXAMPLE 2

The procedure of Example 1 was repeated exactly, except that 171 partsof emulsion (A) were used without incorporating the 40 parts of organiclatex. The final dispersion had a solids content of 72% and a pH of 9.

The mechanical properties and the assessmenets of adhesion are reportedin Table 1 below.

It will be seen that the compositions of the invention exhibitedimproved mechanical and adhesion properties when compared with thecontrol of Comparative Example 2.

                  TABLE 1                                                         ______________________________________                                                                 COMPARATIVE                                                          EXAMPLE 1                                                                              EXAMPLE 2                                                            Parts by weight                                                                        Parts by weight                                      ______________________________________                                        Emulsion (A)      131        171                                              Organic latex     40         0                                                Aqueous solution containing 40% of                                                              7          7                                                potassium methylsiliconate                                                    Dioctyltin dilaurate emulsion                                                                   2.6        2.6                                              Precipitated CaCO.sub.3 (φ ≃ 70 nm)                                           80         80                                               pH                9          9                                                Hardness (Shore A)                                                                              40         23                                               TS (MPa)          1.23       1.02                                             EB (%)            381        639                                              100% modulus (MPa)                                                                              0.90       0.31                                             Adhesiveness to:                                                              glass:            +          +                                                concrete:         ++         +                                                ______________________________________                                    

EXAMPLE 3 Preparation of Two Silicone Dispersions for Paints (a₁) and(a₂)

3.a₁.--Preparation of Tin-Catalyzed Dispersion (a₁):

An emulsion (A) was prepared by polymerizing 1,000 g of anα,ω-(dihydroxy)polydimethylsiloxane oil having a viscosity of 100 mPa.sat 25° C. in the presence of 30 g of dodecylbenzenesulfonic acid and 50g of Cemulsol® ON 10/20, which is a nonionic surfactant, namely, apolyoxyalkylenated compound containing 10 ethylene oxide units and 20propylene oxide units.

The emulsion polymerization was terminated by neutralizing the catalystwith 14.5 g of triethanolamine when the viscosity of the oil reached900,000 mPa.s at 25° C.

To 171 parts of the emulsion (A) were added 7 parts of a solution ofpotassium methylsiliconate having a solids content of 40% and 2.6 partsof aqueous emulsion containing 37% by weight of di-n-octyltin dilaurate.The dispersion (a₁) was thus obtained.

3.a₂.--Preparation of catalyzed dispersion (a₂):

The procedure described in 3.a₁. was repeated exactly, except that the2.6 parts of tin emulsion were not added.

EXAMPLE 4 Preparation of a Tin-Catalyzed Silicone/Styrene/Acrylic LatexMixed Paint

The following constituents were introduced in succession into a kneader:

(i) Water: 10 parts

(ii) Sodium hexametaphosphate in aqueous solution at a concentration of10%: 2 parts

(iii) Xanthan gum marketed by Rhone-Poulenc under the trademarkRhodopol® 23 in aqueous solution at a concentration of 0.4%: 5 parts

(iv) Titanium dioxide marketed by Rhone-Poulenc under the trademarkRex®: 12.5 parts

(v) Talc marketed by "Les Talcs de Luzenac" under the trademark 20MO®:3.6 parts

(vi) Calcium carbonate marketed by Omya under the trademark Durcal® 5:14.5 parts

(vii) Barium sulfate marketed by SCZ under the trademark Rutenia®: 7parts

(viii) Dispersion (a₁): 19.6 parts

(ix) Styrene/acrylic latex (Rhodopas® DS910 employed in Example 1): 15.5parts

(x) Polyacrylate thickener: 2 parts

Finally, there was added:

(xi) Water: 7.9 parts

A tin-catalyzed silicone/styrene/acrylic latex mixed paint was thusobtained.

COMPARATIVE EXAMPLE 5c Preparation of a Pure Silicone Paint

The procedure of Example 4 was repeated exactly except that the 15.5parts of styrene/acrylic latex were replaced with 13.4 additional partsof silicone dispersion (a₁).

EXAMPLE 6 Preparation of a Silicone/Styrene/Acrylic Latex Mixed Paintnot Catalyzed with Tin

To prepare this paint, the procedure of Example 4 was repeated exactly,except that the 19.6 parts of (a₁) were replaced with 19.6 parts of(a₂).

COMPARATIVE EXAMPLE 7C Preparation of a Pure Silicone Paint notCatalyzed with Tin

To prepare this paint, the procedure of Example 6 was repeated exactly,except that the 15.5 parts of styrene/acrylic latex were replaced with13.4 additional parts of silicone dispersion (a₂).

COMPARATIVE EXAMPLE 8C Preparation of a Pure Styrene/Acrylic Latex Paint

To prepare this paint, the procedure of Example 6 was repeated exactly,except that the 19.6 parts of dispersion (a₁) were replaced with 22.5additional parts of styrene/acrylic latex DS910.

EXAMPLE 9 Evaluation of the Water Vapor Permeability of Dried PaintFilms Prepared According to the Procedure of Examples 4, 5C, 6, 7C and8C

Measurements of porosity to water vapor were carried out by according tothe procedure of AFNOR Standard NF T30 704.

These paints (having a weight ratio of pigment+fillers to binder ofapproximately 2/1) were applied onto a fibro-cement substrate. Theweight loss of a glass dish (80 mm height, 170 mm diameter) containing awater reserve and sealed by the painted test specimen was measured every24 hours. The entire assembly was placed in an enclosure maintained at23° C.

The respective porosities P, expressed in g/m² per 7 days of test, arereported in Table 2 below.

From Table 2 below, it will be seen that the paints according to theinvention have a porosity close to the pure silicone paint 7C.

Evaluation of the Wet Abrasion Behavior of the Paints Prepared Accordingto the Procedure of Examples 4, 5C, 6, 7C and 8C

This wet abrasion behavior was evaluated according to DIN Standard53778, by rubbing a paint film provided with certain soiling andscrubbed with a brush using a back-and-forth motion under certainconditions.

The wet abrasion behavior was assessed as the number N of cyclesperformed by the brush to reduce the thickness of the coat of paint by50%.

The results obtained are reported in Table 2 below, from which it willbe seen that the paints according to the invention exhibited a wetabrasion resistance which was much superior to the all-silicone paintsof Examples 5C and 7C.

                  TABLE 2                                                         ______________________________________                                                EXAMPLE                                                                       4      5C     6        7C   8C                                        ______________________________________                                        POROSITY  290      350    310    370  210                                     g/m.sup.2                                                                     N         900      150    500     50  >10,000                                 ______________________________________                                    

EXAMPLE 10

An emulsion (A) was prepared by polymerizing 1,000 g of anα,ω-(dihydroxy)polydimethylsiloxane oil having a viscosity of 100 mPa.sat 25° C. in the presence of 30 g of dodecylbenzenesulfonic acid and 50g of Cemulsol^(R) ON 10/20, which is a nonionic surfactant, namely, apolyoxyalkylenated compound with approximately 10 ethylene oxide unitsand 20 propylene oxide units.

The emulsion polymerization was terminated by neutralizing the catalystwith 14.5 g of triethanolamine when the viscosity of the oil reached300,000 mPa.s at 25° C.

The emulsion (A) obtained had a solids content of 60%.

In the case of each additive, the following constituents wereincorporated under stirring for 10 minutes, in 158 parts of emulsion(A):

(i) 7 parts of polyvinyl acetate emulsion forming a film at atemperature above 15° C., marketed by Rhone-Poulenc under the trademarkRhodopas AO15, which had the following characteristics:

Solids content: 62%

Viscosity at 25° C.: 3,500 mPa.s

Diameter of twin-population particles: 0.1-0.3 μm and 1.5-3 μm;

(ii) 2.2 parts of 50% strength potassium hydroxide solution;

(iii) 7 parts of a hydroxylated silicone resin introduced as such,containing 2.2% by weight of hydroxyl groups, comprising 70% by weightof CH₃ SiO₁.5 units and 30% by weight of (CH₃)₂ SiO units. This resinwas soluble in toluene and had a molecular weight of approximately 1,300and a CH₃ /Si molar ratio=1.77;

(iv) 2.6 parts of an aqueous emulsion containing 37% by weight ofdi-n-octyltin dilaurate;

(v) 100 parts of precipitated CaCO₃ having a mean particle size of 70nanometers.

The final mixture was homogenized for another 30 minutes at a reducedpressure of 1.33 kPa.

The final dispersion had a solids content of 75% and a pH of 9.

The mechanical properties and the quality of the adhesions were measuredaccording to the method described in Example 1, together with the flowthreshold in Pa, measured with a Carrimed^(R) viscometer.

The results obtained are reported in Table 3 below.

COMPARATIVE EXAMPLE 11

The procedure of Example 10 was repeated exactly, except that the 7parts of polyvinyl alcohol emulsions were not incorporated. The finaldispersion had a solids content of 76% and pH of 9.

The mechanical properties and the assessments of adhesion are reportedin Table 3 below.

EXAMPLE 12 AND 13

The procedure of Example 10 was repeated, except that 20 and 40 parts ofpolyvinyl alcohol emulsion were introduced, respectively.

The results obtained are reported in Table 3 below.

                  TABLE 3                                                         ______________________________________                                                Comparative                 Example                                           Example 11                                                                            Example 10                                                                              Example 12                                                                              13                                                parts by                                                                              parts by  parts by  parts by                                          weight  weight    weight    weight                                    ______________________________________                                        Emulsion (A)                                                                            158       158       158     158                                     Rhodopas AO15                                                                           0         7         20      40                                      Silicone resin                                                                          7         7         7       7                                       Dioctyltin                                                                              2.6       2.6       2.6     2.6                                     dilaurate                                                                     emulsion                                                                      Precipitated                                                                            100       40        100     100                                     CaCO.sub.3                                                                    (φ ≃ 70 nm)                                                 KOH (50%) 2.2       2.2       2.2     2.2                                     pH        9         9         9       9                                       Hardness  34        28        28      28                                      (Shore A)                                                                     TS (MPa)  1.66      1.23      1.35    1.11                                    EB (%)    784       687       787     894                                     100% modulus                                                                            0.40      0.32      0.32    0.34                                    (MPa)                                                                         Flow threshold                                                                          173       256       334     --                                      (Pa)                                                                          Adhesiveness to:                                                              glass:    x         xx        xx      xx                                      concrete: x         xx        xx      xx                                      ______________________________________                                    

EXAMPLES 14 TO 17 AND COMPARATIVE EXAMPLES 18 AND 19 Preparation of theMill Base (A14)

The following materials were mixed under stirring:

(i) 909 parts of an α,ω-dihydroxypolydimethylsiloxane oil having aviscosity of 160 mPa.s at 25° C.;

(ii) 45.4 parts of the nonionic surfactant Cemulsol® NP12(polyethoxylated nonylphenol), marketed by Rhone-Poulenc;

(iii) 45.6 g of distilled water, added slowly over 15 minutes.

The mixture obtained was passed through the colloid mill and 1,000 partsof mill base were obtained.

Preparation of the Emulsion E14

To 500 parts of the mill base (A14) thus obtained were added 50 parts ofa styrene/alkyl acrylate latex marketed by Rhone-Poulenc under thetrademark Rhodopas® DEA913 which had the following characteristics:

Film-forming at a temperature above 16° C.:

Solids content: 38%

Particle size: 0.05 μm

pH=8.5

Brookfield viscosity (50 revolutions per minute): 250 mPa.s.

67 parts of water were then added and then, very rapidly, 79 parts of anaqueous solution containing 20% by weight of dodecylbenzenesulfonic acid(DBSA). Stirring was continued for 3 hours and the mixture was thenpermitted to polymerize while standing for an additional 21 hours. Atthe end of polymerization, it was neutralized with 15.9 parts of anaqueous solution containing 50% by weight of triethanolamine to obtainemulsion E14, whose final composition and characteristics are reportedin Table 4 below.

Preparation of Emulsion E15

500 parts of mill base (A14) were diluted with 50 parts of Rhodopas®DEA93 latex and then with 89 parts of an aqueous solution containing14.83 by weight of sodium laurylsulfate and, finally, with 48.4 parts ofdistilled water. After stirring, 7.6 parts of an aqueous solutioncontaining 22% by weight of hydrochloric acid (HCl) were introduced toinitiate the polymerization.

After 24 hours of standing at 25° C., the mixture was neutralized with13.7 g of triethanolamine at a concentration of 50% by weight in water.The final composition and the characteristics of the emulsion E15 thusobtained are reported in Table 4 below.

Preparation of Emulsion E16

The procedure was exactly the same as for preparing emulsion E15, exceptthat:

(i) 100 parts of Rhodopas® were added;

(ii) no distilled water was added.

Preparation of Emulsion E17

This was obtained by diluting emulsion (E16) with an appropriate amountof distilled water.

Preparation of Emulsion E18

The procedure for preparing emulsion (E14) was repeated, except that nolatex was introduced.

Preparation of Emulsion E19

The procedure for preparing emulsion (E15) was repeated, except that nolatex was introduced.

The compositions and the characteristics of emulsions E14 to E19 arereported in Table 4 below. Comparison of the solids contents and of thecorresponding viscosities, measured with a Rheomat® 30 viscometer at 25°C. at a shear rate of 1 s⁻¹, illustrates the advantage of thetwin-population emulsions E14 to E17, which made it possible to obtainhigh solids contents, typically desirable for applications in theconstruction industry, while preserving the low viscosity values whichare compatible with the processes for preparing the filled finaldispersion.

                  TABLE 4                                                         ______________________________________                                                EXAMPLE                                                                       14   15      16      17    18    19                                           EMULSION                                                                      E14  E15     E16     E17   E18   E19                                  ______________________________________                                        Compositions:                                                                 parts by weight                                                               Hydroxylated                                                                            652.2  641.3   641   596.5 636.9 637                                silicone oil                                                                  Cemulsol NP12                                                                           32.6   32      32    29.8  31.8  31.8                               Sodium    --     18.6    18.7  17.4  --    18.6                               laurylsulfate                                                                 DBSA      22.8   --      --    --    22.3  --                                 Pure HCl  --     2.4     2.4   2.2   --    2.4                                Pure tri- 11.4   9.7     9.7   9.0   11.2  9.7                                ethanolamine                                                                  Water     253.8  225.5   155.2 213.8 297.8 300.5                              Rhodopas  27.2   70.5    141   131   --    --                                 DEA913                                                                        latex                                                                         Characteristics:                                                              Measured solids                                                                         74.6   73.85   76.3  71    71    71.6                               content (%)                                                                   M.S.C.                                                                        Calculated solids                                                                       73.0   73.1    75.8  --    --    --                                 content (%)                                                                   C.S.C.                                                                        Viscosity of the                                                                        110    150     90    90    320   220                                silicone                                                                      polymer (Pa · s)                                                     Viscosity of the                                                                        28     28      27    14.8  52    50                                 emulsion at                                                                   1 s.sup.-1 (Pa · s)                                                  M.S.C./emulsion                                                                         2.66   2.64    2.06  4.80  1.36  1.43                               viscosity ratio                                                               ______________________________________                                    

EXAMPLE 20 AND COMPARATIVE EXAMPLE 21 Formulation of Filled AqueousDispersions D14 and D18 Preparation of Dispersion D14

The following ingredients were added in this order to a 5-liter Meili®type bladed kneader, an incorporation period of 10 minutes beingobserved each time a new ingredient was introduced:

(i) 134 parts of emulsion (E14);

(ii) 2 parts of an aqueous solution containing 50% by weight ofpotassium hydroxide;

(iii) 0.52 parts of an aqueous emulsion containing 37% by weight ofdi-n-octyltin dilaurate;

(iv) 100 parts of precipitated CaCO₃ having a mean particle size of 70nonometers;

(v) 7 parts of the same hydroxylated silicone resin as that employed inExample 10.

The final mixture obtained was homogenized for an additional 30 minutesunder a reduced pressure of 1.33 kPa.

The composition obtained was stored in an airtight cartridge and at roomtemperature for about 15 days. The mechanical properties were measuredby following the procedure of Example 1, except that the film ofelastomer was permitted to dry for 15 days.

The composition of D14 and its mechanical properties are reported inTable 5 below.

Preparation of Dispersion (D18)

The procedure employed for (D14) was repeated exactly, except that 141parts of emulsion (E18) were employed.

The composition of D18 and its mechanical properties are reported inTable 5 below.

From Table 5, it will be seen that an elastomer which had mechanicalproperties similar to those obtained from D18 was obtained with D14.

                  TABLE 5                                                         ______________________________________                                                           EXAMPLE                                                                       20    21                                                   ______________________________________                                        Composition (in parts by weight)                                                                   D14     D18                                              Emulsion D14         134     --                                               Emulsion D18         --      141                                              50% KOH solution     2       2                                                Sn emulsion          0.52    0.52                                             CaCO.sub.3           100     100                                              Silicone resin       7       7                                                Pourability (Boeing test) in mm                                                                    0       0                                                Shore A hardness     30      28                                               TS (MPa)             30      28                                               EB (%)               678     908                                              100% modulus (MPa)   0.55    0.40                                             ______________________________________                                    

EXAMPLE 22

An emulsion (A) was prepared by polymerizing 1,000 g of anα,ω-(dihydroxy)polydimethylsiloxane oil having a viscosity of 100 mPa.sat 25° C. in the presence of 30 g of dodecylbenzenesulfonic acid and 50g of Cemulsol® ON 10/20, marketed by Rhone-Poulenc, which is a nonionicsurfactant, namely, a compound polyoxyalkylenated with approximately 10ethylene oxide units and 20 propylene oxide units.

The emulsion polymerization was terminated by neutralizing the catalystwith 14.5 g of triethanolamine when the oil viscosity reached 300,000mPa.s at 25° C.

The emulsion (A) obtained had a solids content of 60%.

In the case of each additive, the following constituents wereincorporated in 158 parts of emulsion (A), under stirring for 10minutes:

(i) 7 parts of a nonfilm-forming polystyrene/homopolymer latex which hadthe following characteristics:

Solids content: 50%

pH: 8

Viscosity at 25° C. (50 revolutions/min): less than 100 mPa.s

Particle diameter: ≅0.45 μm;

(ii) 2.2 parts of a 50% potassium hydroxide solution;

(iii) 7 parts of a hydroxylated silicone resin introduced as such,containing 2.2% by weight of hydroxyl groups, comprising 70% by weightof CH₃ SiO₁.5 units and 30% by weight of (CH₃)₂ SiO units. This resinwas soluble in toluene and had a molecular weight of approximately 1,300and a CH₃ /Si molar ratio=1.77;

(iv) 2.6 parts of aqueous emulsion containing 37% by weight ofdi-n-octyltin dilaurate;

(v) 100 parts of precipitated CaCO₃ having a mean particle size of 70nonometers.

The final mixture was homogenized for an additional 30 minutes at areduced pressure of 1.33 kPa.

The final dispersion had a solids content of 75% and a pH of 8.5.

After 7 days of storage, the dispersion was spread with a doctor bladeinto a 2-mm thick film which was permitted to dry at room temperature(20° C.) for 10 days.

The following average mechanical properties were measured on a firstbatch of dried films:

(a) Shore A hardness (SAM) according to ASTM Standard D-2240;

(b) Tensile strength (TS) according to AFNOR Standard T-46 002corresponding to ASTM Standard D 412, in MPa;

(c) Elongation at break (EB) in % according to AFNOR Standard T 46 002;

(d) Elasticity modulus (EM) at 100% elongation according to AFNORStandard T 46 002, in MPa;

(e) Flow threshold in Pa, measured in a Carrimed® viscometer.

The mechanical properties obtained are reported in Table 6 below.

To assess adhesiveness, a 4-mm thick bead of aqueous dispersion wasdeposited onto a glass or concrete support. After 12 days, theadhesiveness of the elastomer formed was assessed by pulling the bead byhand.

The adhesions were qualified in three ways:

(1) good adhesiveness when the bead could not be stripped from itssupport (indicated as ++);

(2) average adhesiveness when the bead is stripped with difficulty andover small areas (indicated as +);

(3) absence of adhesiveness when the bead is stripped easily (indicatedas 0).

The assessments of adhesion are reported in Table 6 below.

COMPARATIVE EXAMPLE 23

The procedure of Example 1 was repeated exactly, except that the 7 partsof organic latex were not incorporated. The final dispersion had asolids content of 76% and a pH of 9.

The mechanical properties and the assessments of adhesion are reportedin Table 6 below.

EXAMPLE 24

The procedure of Example 22 was repeated exactly, except that 20 partsof organic latex were incorporated. The final dispersion had a solidscontent of 74% and a pH of 9.

The mechanical properties and the assessments of the adhesion arereported in Table 6 below.

EXAMPLE 25

The operating procedure of Example 22 was repeated exactly, except thata nonfilm-forming polystyrene homopolymer latex was employed, marketedby Rhone-Poulenc under the trademark Rhodopas SO51®, which had thefollowing characteristics:

Solids content: 50%

pH: 8

Brookfield viscosity at 23° C. (50 revolutions/min): 150 mPa.s

Particle diameter: approximately 0.16 μm.

The results obtained are reported in Table 7 below.

EXAMPLES 26 AND 27

The procedure of Example 25 was repeated exactly, except that 20 and 40parts of Rhodopas SO51® organic latex were introduced, respectively.

The results obtained are reported in Table 7 below.

                  TABLE 6                                                         ______________________________________                                                           COMPARA-                                                                      TIVE                                                                 EXAMPLE 22                                                                             EXAMPLE 23 EXAMPLE 24                                                parts by parts by   parts by                                                  weight   weight     weight                                          ______________________________________                                        Emulsion (A)                                                                              158        158        158                                         Organic latex                                                                             7          0          20                                          Silicone resin                                                                            7          7          7                                           Dioctyltin dilaurate                                                                      2.6        2.6        2.6                                         emulsion                                                                      Precipitated CaCO.sub.3                                                                   100        100        100                                         (φ ≃ 70 nm)                                                 KOH (50%)   2.2        2.2        2.2                                         pH          9          9          9                                           Hardness    34         34         33                                          (Shore A)                                                                     TS (MPa)    1.27       1.66       1.37                                        EB (%)      611        784        680                                         100% modulus (MPa)                                                                        0.50       0.40       0.52                                        Flow threshold (Pa)                                                                       190        174        252                                         Adhesiveness to:                                                              glass:      ++         +          ++                                          concrete:   ++         +          ++                                          ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                                COMPARA-                                                                      TIVE                                                                          EXAMPLE EXAMPLE   EXAMPLE   EXAM-                                             23      25        26        PLE 27                                            parts by                                                                              parts by  parts by  parts by                                          weight  weight    weight    weight                                    ______________________________________                                        Emulsion (A)                                                                            158       158       158     158                                     Organic latex                                                                           0         7         20      40                                      Silicone resin                                                                          7         7         7       7                                       Dioctyltin                                                                              2.6       2.6       2.6     2.6                                     dilaurate                                                                     emulsion                                                                      Precipitated                                                                            100       100       100     100                                     CaCO.sub.3                                                                    (φ ≃ 70 nm)                                                 KOH (50%) 2.2       2.2       2.2     2.2                                     pH        9         9         9       9                                       Hardness  34        30        30      32                                      (Shore A)                                                                     TS (MPa)  1.66      1.42      1.28    1.31                                    EB (%)    784       746       808     904                                     100% modulus                                                                            0.40      0.43      0.43    0.33                                    (MPa)                                                                         Flow threshold                                                                          174       261       303     --                                      (Pa)                                                                          Adhesiveness to:                                                              glass:    +         ++        ++      ++                                      concrete: +         ++        ++      ++                                      ______________________________________                                    

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What claimed is:
 1. A substrate coated with an aqueous siliconedispersion crosslinkable into an elastomeric state on removal of watertherefrom under ambient conditions, said aqueous silicone dispersioncomprising:(A) an oil-in-water base emulsion of anα,ω-(dihydroxy)polydiorganosiloxane stabilized with at least one anionicor nonionic surface-active agent, or mixture thereof; (B) an aqueouslatex of an organic homopolymer of alkyl (meth)acrylate,α,β-ethylenically unsaturated ester of a monocarboxylic acid, the acidmoiety of which is not polymerizable, ester or half-ester of anα,β-ethylenically unsaturated polycarboxylic acid, vinyl halide,vinylaromatic, conjugated aliphatic diene, or α,β-ethylenicallyunsaturated nitrile; (C) an effective crosslinking amount of at leastone crosslinking agent for reacting with the emulsion (A) to produce anelastomeric state; and (D) at least one nonsiliceous filler material inan amount effective for semi-reinforcement or packing.
 2. The substrateas defined by claim 1, coated with from 20 to 100 g of said aqueoussilicone dispersion per m² of surface thereof.
 3. The substrate asdefined by claim 1, wherein said organic homopolymer is polyvinylacetate or polystyrene.
 4. The substrate as defined by claim 1, whereinsaid aqueous latex (B) has a particle size ranging from 0.01 to 0.5 μmand a solids content ranging from 20% to 70% by weight.
 5. The substrateas defined by claim 1, wherein said aqueous silicone dispersion has asolids content of at least 40% by weight.
 6. The substrate as defined byclaim 1, wherein said aqueous silicone dispersion comprises 100 parts byweight of said stabilized oil-in-water emulsion (A), from 2 to 80 partsby weight of said aqueous latex (B), and from 5 to 200 parts by weightof said at least one nonsiliceous filler material (D).
 7. The substrateas defined by claim 6, wherein said aqueous silicone dispersioncomprises from 3 to 40 parts by weight of said aqueous latex (B), andfrom 50 to 150 parts by weight of said at least one nonsiliceous fillermaterial (D).
 8. The substrate as defined by claim 1, wherein said atleast one nonsiliceous filler material (D) comprises calcium carbonate,carbon black, titanium dioxide, aluminum oxide, hydrated alumina,expanded vermiculite, hydrated borax, unexpanded vermiculite, zincoxide, mica, talc, iron oxide, barium sulfate, slaked lime, or mixturesthereof.
 9. The substrate as defined by claim 8, wherein said at leastone nonsiliceous filler material (D) comprises precipitated calciumcarbonate having a mean particle diameter of less than 0.1 μm.
 10. Asubstrate coated with an aqueous silicone dispersion crosslinkable intoan elastomeric state on removal of water therefrom under ambientconditions, said aqueous silicone dispersion comprising:(A) anoil-in-water base emulsion of an α,ω-(dihydroxy)polydiorganosiloxanestabilized with at least one anionic or nonionic surface-active agent,or mixture thereof; (B) an aqueous latex of an organic polymercomprising at least two different monomers selected from the groupconsisting of alkyl (meth)acrylates, α,β-ethylenically unsaturatedesters of a monocarboxylic acid, the acid moiety of which is notpolymerizable, esters or half-esters of an α,β-ethylenically unsaturatedpolycarboxylic acid, vinyl halides, vinylaromatics, conjugated aliphaticdienes, α,β-ethylenically unsaturated nitriles, ethylenic monomerscontaining secondary, tertiary or quaternized amine groups, sulfonatedethylenic monomers, zwitterionic ethylenic monomers, amides ofunsaturated carboxylic acids, and esters of polyhydroxypropyl orpolyhydroxyethylated alcohols; (C) an effective crosslinking amount ofat least one crosslinking agent for reacting with the emulsion (A) toproduce an elastomeric state; and (D) at least one nonsiliceous fillermaterial in an amount effective for semi-reinforcement or packing. 11.The substrate as defined by claim 10, coated with from 20 to 100 g ofsaid aqueous silicone dispersion per m² of surface thereof.
 12. Thesubstrate as defined by claim 10, wherein said organic polymer is astyrene/alkyl acrylate copolymer in which the styrene/acrylate weightratio ranges from 30/70 to 70/30.
 13. The substrate as defined by claim10, wherein said aqueous latex (B) has a particle size ranging from 0.01to 0.5 μm and a solids content ranging from 20% to 70% by weight. 14.The substrate as defined by claim 10, wherein said aqueous siliconedispersion has a solids content of at least 40% by weight.
 15. Thesubstrate as defined by claim 10, wherein said aqueous siliconedispersion comprises 100 parts by weight of said stabilized oil-in-wateremulsion (A), from 2 to 80 parts by weight of said aqueous latex (B),and from 5 to 200 parts by weight of said at least one nonsiliceousfiller material (D).
 16. The substrate as defined by claim 15, whereinsaid aqueous silicone dispersion comprises from 3 to 40 parts by weightof said aqueous latex (B), and from 50 to 150 parts by weight of said atleast one nonsiliceous filler material (D).
 17. The substrate as definedby claim 10, wherein said at least one nonsiliceous filler material (D)comprises calcium carbonate, carbon black, titanium dioxide, aluminumoxide, hydrated alumina, expanded vermiculite, hydrated borax,unexpanded vermiculite, zinc oxide, mica, talc, iron oxide, bariumsulfate, slaked lime, or mixtures thereof.
 18. The substrate as definedby claim 17, wherein said at least one nonsiliceous filler material (D)comprises precipitated calcium carbonate having a mean particle diameterof less than 0.1 μm.
 19. A substrate coated with an aqueous siliconedispersion crosslinkable into an elastomeric state on removal of watertherefrom under ambient conditions, said aqueous silicone dispersioncomprising:(A) an oil-in-water base emulsion of anα,ω-(dihydroxy)polydiorganosiloxane stabilized with at least one anionicor nonionic surface-active agent, or mixture thereof; (B) an aqueouslatex of an organic polymer which consists of alkyl (meth)acrylate,α,β-ethylenically unsaturated ester of a monocarboxylic acid, the acidmoiety of which is not polymerizable, ester or half-ester of anα,β-ethylenically unsaturated polycarboxylic acid, vinyl halide,vinylaromatic, conjugated aliphatic diene, α,β-ethylenically unsaturatednitrile monomer, ethylenic monomers containing secondary, tertiary orquaternized amine groups, sulfonated ethylenic monomers, zwitterionicethylenic monomers, amides of unsaturated carboxylic acids, esters ofpolyhydroxypropyl or polyhydroxyethylated alcohols, or combinationsthereof; (C) an effective crosslinking amount of at least onecrosslinking agent for reacting with the emulsion (A) to produce anelastomeric state; and (D) at least one nonsiliceous filler material inan amount effective for semi-reinforcement or packing.
 20. The substrateas defined by claim 19, coated with from 20 to 100 g of said aqueoussilicone dispersion per m² of surface thereof.
 21. The substrate asdefined by claim 19, wherein said organic polymer is a styrene/alkylacrylate copolymer in which the styrene/acrylate weight ratio rangesfrom 30/70 to 70/30, a polyvinyl acetate, or a polystyrene.
 22. Thesubstrate as defined by claim 19, wherein said aqueous latex (B) has aparticle size ranging from 0.01 to 0.5 μm and a solids content rangingfrom 20% to 70% by weight.
 23. The substrate as defined by claim 19,wherein said aqueous silicone dispersion has a solids content of atleast 40% by weight.
 24. The substrate as defined by claim 19, whereinsaid aqueous silicone dispersion comprises 100 parts by weight of saidstabilized oil-in-water emulsion (A), from 2 to 80 parts by weight ofsaid aqueous latex (B), and from 5 to 200 parts by weight of said atleast one nonsiliceous filler material (D).
 25. The substrate as definedby claim 24, wherein said aqueous silicone dispersion comprises from 3to 40 parts by weight of said aqueous latex (B), and from 50 to 150parts by weight of said at least one nonsiliceous filler material (D).26. The substrate as defined by claim 19, wherein said at least onenonsiliceous filler material (D) comprises calcium carbonate, carbonblack, titanium dioxide, aluminum oxide, hydrated alumina, expandedvermiculite, hydrated borax, unexpanded vermiculite, zinc oxide, mica,talc, iron oxide, barium sulfate, slaked lime, or mixtures thereof. 27.The substrate as defined by claim 26, wherein said at least onenonsiliceous filler material (D) comprises precipitated calciumcarbonate having a mean particle diameter of less than 0.1 μm.
 28. Thesubstrate as defined by claim 19, wherein said aqueous dispersion has(i) a first population of particles originating from said aqueous latex(B) having a particle size ranging from about 0.01 μm to about 0.15 μmand (ii) a second population of particles originating from saidoil-in-water emulsion (A) having a particle size ranging from 0.15 μm to100 μm.
 29. The substrate as defined by claim 28, wherein said aqueousdispersion has (iii) a solids content of more than 60% by weight, and(iv) a viscosity of less than 50,000 in mPa.s at 25° C., measured at ashear rate of 1 s⁻¹ prior to incorporation of the nonsiliceous fillermaterial (B).
 30. The substrate as defined by claim 29, wherein saidaqueous latex (B) has a solids content of from about 20% to about 40% byweight.